257950-84-8

Upstream product

• 286-20-4 cyclohexene oxide 
• 298-06-6 O,O-Diethyl hydrogen phosphorodithioate 
• 257950-77-9 (-)-(1R,2R,S_S,1'R,2'S,3'R)-trans-2-(4-methoxybenzyl)-nopylsulfinylcyclohexanol 

Relevant academic research and scientific papers

An oxorhenium complex bearing a chiral cyclohexane-1-olato-2-thiolato ligand: Synthesis, stereochemistry, and theoretical study of parity violation vibrational frequency shifts

In our effort towards measuring the parity violation energy difference between two enantiomers, a simple chiral oxorhenium complex 5 bearing enantiopure 2-mercaptocyclohexan-1-ol has been prepared as a potential candidate species. Vibrational circular dichroism revealed a chiral environment surrounding the rhenium atom, even though the rhenium is not a stereogenic center itself, and enabled to assign the (1S,2S)-(?) and (1R,2R)-(+) absolute configuration for 5. For both compound 5 and complex 4, previously studied by us and bearing a propane-2-olato-3-thiolato ligand, relativistic calculations predict parity violating vibrational frequency differences of a few hundreds of millihertz, above the expected sensitivity attainable by a molecular beam Ramsey interferometer that we are constructing.

Catalytic asymmetric synthesis of thiols

The synthesis of enantiopure thiols is of significant interest for industrial and academic applications. However, direct asymmetric approaches to free thiols have previously been unknown. Here we describe a novel organocascade that is catalyzed by a confined chiral phosphoric acid and furnishes O-protected β-hydroxythiols with excellent enantioselectivities. The method relies on an asymmetric thiocarboxylysis of meso-epoxides, followed by an intramolecular trans-esterification reaction. By varying the reaction conditions, the intermediate thioesters can also be obtained chemoselectively and enantioselectively.

Chiral phosphoric acid catalyzed enantioselective desymmetrization of meso-epoxides by thiols

The first chiral Bronsted acid catalyzed asymmetric nucleophilic ring-opening reaction of meso-epoxides is described. In the presence of TRIP, a range of meso-epoxides could undergo smooth ring-opening reactions by aryl thiols with good efficiency and enantioselectivity.

Regio- and stereoselective ring-opening of epoxides using organic dithiophosphorus acids as nucleophiles

A practical method for the synthesis of β-hydroxymercaptans has been successfully developed through the ring-opening of epoxides with organic dithiophosphorus acids 1. Highly regio- and stereoselective products, β-hydroxyalkyl dithiophosphates, which were transformed to the corresponding synthetically valuable β-hydroxymercaptans by further reduction, were obtained under mild reaction conditions without any catalyst or promoter. Highly enantioselective ring-opening reaction of cyclohexene epoxide with 1 was realized in the presence of a chiral (salen)Ti(IV) complex.

The cleavage of meso-epoxides with homochiral thiols: Synthesis of (+)- and (-)-trans-1-mercaptocyclohexan-2-ol

The synthesis of (+)- and (-)-trans-1-mercaptocyclohexan-2-ol is described. Ring opening of cyclohexene oxide with (-)-4-methoxybenzylnopan- 3(R)-thiol 1a followed by oxidation gives two readily separable diastereomeric sulfoxides. These sulfoxides display very different thermal stability but both undergo regio-specific syn-elimination to give cyclohexan- 1-ol-2-sulfenic acid that can be reacted in situ with 3,5-dimethylthiophenol to give a mixed disulfide. Reduction of these disulfides with lithium aluminium hydride gives the title compounds in enantiomerically pure form.